CH635227A5 - Parasitenbekaempfungsmittel. - Google Patents

Description

635227

2nd

PATENT CONTROL Parasiticide, characterized in that it is a new compound of the formula

] TVch2n ^ r <xe

- R3 (X)

where R.! Alkyl having 1 to 3 carbon atoms or hydrogen, R2 and R3 are alkyl or hydroxyalkyl having 1 to 4 carbon atoms, or R2 and R3 together with the nitrogen atom to which they are attached are a radical of the formula y hs

(II)

form in which W is the methylene group or an oxygen atom, Z is a hydrogen atom, U and T are methyl radicals or hydrogen atoms or T and Z together represent an oxygen atom.

R4 is alkyl having 1 to 18 carbon atoms, X is a halogen atom, Y is hydroxyl, alkoxy, alkyl or nitro group and n is 0 to 4, contains at least one active ingredient.

The use of various substances to control pathogens which cause plant diseases is known.

For this purpose e.g. used as fungicides Benzimida-5 zole. However, it has been found that the multiple use of these highly effective but very selective fungicides leads to a change in the parasitic microflora. Instead of the pathogens destroyed by the benzimidazole derivatives, new pests arise, e.g. B. Mushrooms of the species Alio ternaria, which cause severe plant diseases.

It has unexpectedly been found that the compounds of the formula mentioned above which have not yet been described have a strong action on phatogens which cause plant diseases. The agent according to the invention, which contains the new compounds of general formula I as at least one active ingredient, has a strong effect on pathogenic fungi and bacteria, and also on fungi of the Alternaria species. The effectiveness of the agent according to the invention was investigated with respect to the 20 fungi of the species Alternaria, Botrytis, Rhizoctonia, Fusarium and Aspergillus by comparing the effectiveness of the agent with its known fungicides such as "carbazazim" (2-benzimidazolecarbamic acid methyl ester), "methylthiophanate" (1,2-bis (3-methoxycarbonyl 25 2, -thioureidobenzene) and «tridemorph» (N-tridecyl-2,6-dimethylmorpholine) was compared.

The effectiveness of a preferred compound of the formula

30th

The invention relates to an agent for combating pathogens causing plant diseases, which contains at least one active ingredient component, a new compound of the following formula:

o2nr, c = ch

Y "

H2N \ R X

R3 (i)

Wci wherein Rj is alkyl with 1 to 3 carbon atoms or hydrogen, R2 and R3 are alkyl or hydroxyalkyl with 1 to 4 carbon atoms or R2 and R3 together with the nitrogen atom to which they are attached are a radical of the formula

'U-

Huh

(II)

form in which W is the methylene group or an oxygen atom, Z is a hydrogen atom, U and T are methyl radicals or hydrogen atoms or T and Z together represent an oxygen atom.

R4 is alkyl of 1 to 18 carbon atoms, X is a halogen atom, Y is hydroxy, alkoxy, alkyl or nitro group and n is 0 to 4.

-R2

02NF ^ = CH-4A-CH2Nr-R4 Xe (in) ^ R3

35 was determined by carrying out in vitro investigations on the spores of the Alternaria tenuis fungus from a 4-day culture and the Botrytis cinerea from a 14-day culture. The test results are shown in Table I, with the potency of the compounds given as the lowest concentration that completely suppressed spore germination.

The spore germination of the fungus Alternaria tenuis has already been suppressed by concentrations of the new compounds which are much lower than the required concentrations 45 of the known fungicides, such as "Karbendazim", "Methylthiophanat" and "Tridemorph". Compound No. 11 suppressed spore germination of the fungus at a concentration 100 times smaller than that of known fungicides. Compounds Nos. 3, 5, 11 and 12 had the greatest effectiveness with regard to the fungus Botrytis cinerea, the germination being suppressed at lower concentrations than with "Karbendazim" and "Methylthiophanat". Compound No. 10 acted in the same concentration as "Karbendazim" and "Methyl-55 thiophanate" and in a concentration 100 times lower than Tridemorph.

The effectiveness of preferred compounds of the formula o2nr) c = ch / ^

chjn ^ r4 R3

'0

(IV)

65

was examined in the same manner as that of the compounds of formula III.

The results are shown in Tab. 2.

3 635227

Table 1

Effectiveness of the compounds with the formula (III)

No. of Rj R2 R3 R4 x concentration to sub

Connection pressure of spore germination

(ppm)

Alternaria botrytis tenuis cinerea

1.

-ch3

-ch3 -ch3

-c8h17

Br

> 1000

1000

2nd

-ch3

-ch3 -ch3

—C10h21

cl

+ 1000

100

3rd

-ch3

-ch3 -ch3

~ cx2h25

cl

100

<10> 1

4th

-ch3

-ch3 -ch2ch2oh

-c10h21

cl

100

100

5.

-ch3

-ch3 -ch2ch2oh

—Ci2h25

Cl

100

<10> 1

6.

-ch3

ch2ch2o-ch2ch2-

-c7h15

J

> 1000

+ 100

7.

-ch3

-ch2ch2o-ch2ch2-

-c7h15

Cl

1000

100

8th.

-ch3

-ch2ch2-o-ch2ch2-

—C8Hi7

Cl

+ 100

100

9.

-ch3

—Ch2ch2-o-ch2ch2-

—C10h21

Cl

100

100

10th

-ch3

-ch2ch2-o-ch2ch2-

-c12H25

Cl

100

+ 10

11.

-ch3

-ch2ch2-o-ch2ch2-

-c14h29

Cl

10th

<10> 1

12.

-ch3

-ch2-ch-o-ch-ch2-1 1

cj2h25

Cl

100

<10> 1

ch3 ch3

«Carbendazim»

> 1000

± 10

«Methylthiophanate»

> 1000

+ 10

"Tridemorph"

> 1000

> 1000

Table 2

Effectiveness of the compounds with the formula (IV)

Connection number ri r2

r3

r4

X

Concentration to suppress spore germination (ppm)

Alternaria botrytis tenuis cinerea

13.

-ch3

-ch3

-ch3

—C8h17

Br

> 1000

+ 100

14.

-H

-ch3

-ch3

—Ci0h2I

Cl

100

> 10 <1

15.

-ch3

-ch3

-ch3

-c10h21

Cl

+ 1000

<10> 1

16.

-ch3

-ch3

-ch3

-c12h25

Cl

100

<10> 1

17th

-ch3

-ch3

-ch2ch2oh

-c10h21

Cl

+ 10

<10> 1

18th

-H

-ch3

-ch2ch2oh

—CI2h25

Cl

+ 10

<10> 1

19th

-ch3

-c2h5

-ch2ch2oh cJ2h25

Cl

+ 10

+ 10

20th

-ch3

-ch2ch2och2ch2-

c7hJ 5

Cl

1000

<10> 1

21.

-ch3

-ch2ch2och2ch2-

CgHj7

Cl

100

<10> 1

22.

-ch3

-ch2ch2och2ch2-

—Ci0h2i

Cl

100

<10> 1

23.

-ch3

-ch2ch2och2ch2-

-c12h25

Cl

<10> 1

<10> 1

24th

-ch3

-ch2ch2och2ch2-

~ c1 <). h29

Cl

<10> 1

+ 10

25th

-ch3

—Ch2ch2och2ch2-

-Ci6H33

Cl

+ 10

± 10

«Carbendazim»

> 1000

± 10

«Methylthiophanate»

> 1000

± 10

"Tridemorph"

> 1000

> 1000

With regard to the fungus Alternaria tenuis, the compounds showed a stronger effect than the comparative

17, 18, 19, 23, 24 and 25 a much higher level of gicides.

Efficacy than the comparative fungicides. Regarding the effectiveness of the preferred compounds of the

Mushroom Botrytis cinerea had the majority of the formula examined

_ / 0CH3 / R2

^ _ / - ch2n ^ -r * xe (v)

02nr, c = ch / r '

was examined in the same way as that of formula III compounds. The results are shown in Tab. 3.

635 227 4

Table 3

Efficacy of the compounds with the formula (V)

No. of the Rt R2 R3 R4 X concentration to the sub

Connection pressure of spore germination

(ppm)

Alternaria botrytis tenuis cinerea

26.

-ch3

-ch3 -ch3

-C7H1s

Br

1000

+ 100

27th

-ch3

-ch3 ch3

-c10h21

Cl

+ 100

100

28

-ch3

-ch3 -ch3

~ c12h25

Cl

± 10

<10> 1

29.

-ch3

-ch3 -ch2ch2oh

-CsH17

Cl

+ 100

1000

30th

-ch3

-ch3 -ch2ch2oh

~ qIOh21

Cl

± 1000

± 10

31

-ch3

-ch3 -ch2ch2oh

"ciîhÎS

Cl

± 100

<10> 1

32.

-ch3

-c2h5 -ch2ch2oh

~ CIOH2I

Cl

10th

± 10

33.

-ch3

-c2hs -ch2ch2oh

Cl

<10> 1

<10> 1

34.

-ch3

-ch2ch2och2ch2-

-c7h15

j

> 1000

+ 1000

35.

-ch3

-ch2ch2och2ch2-

-c7h1s

Cl

> 1000

1000

36.

-ch3

-ch2ch2och2ch2-

-c8h17

Cl

100

<10> 1

37.

-ch3

-ch2ch2och2ch2-

-CIOH21

Cl

± 100

<10> 1

38.

-ch3

-ch2ch2och2ch2-

Cl

100

<10> 1

39.

-ch3

-ch2ch-o-ch2ch2-1 \

-CI2h2s

Cl

100

<10> 1

ch3 ch3

«Carbendazim»

> 1000

± 10

«Methylthiophanate»

> 1000

± 10

"Tridemorph"

> 1000

> 1000

The activity of the majority of the compounds examined with regard to the fungus Alternaria tenuis exceeds that of the comparative fungicides, in particular the compound no. 32 is characterized by a high activity. With regard to the Botrytis cinerea fungus, the majority of the new compounds are more effective than the comparative fungicides.

The compounds represented by the general formula I can be quaternized by tertiary amines of the formula R2R3R4N, where R2, R3 and R4 have the meaning given above, with appropriately substituted halomethyl-β-nitro-β-alkylstyrenes or halomethyl-β- nitrostyrenes can be obtained. The quaternization can in solution in such solvents as. B. benzene, acetone, 45 dimethylformamide, or in mixtures of solvents. The majority of the tertiary amines could be obtained by alkylation of secondary amines by known methods and the amine derivatives of 2-oxomorpholine were usually prepared by alkylation 50 and cyclization of the corresponding monoalkylaminoethanol with chloroacetic acid esters.

The compounds defined by formula I can also be synthesized by quaternization with haloalkylenes of corresponding N, N-dialkyl- (β-nitroalkenyl) benzylamines. The compounds of the formula I have the typical chemical properties of the ammonium salts and are water-soluble, which makes their use easier.

The agent according to the invention can be used in the form of 60 water solutions, suspension powders, concentrated powders for dusting, emulsions, pastes or tablets. For this purpose, the active ingredient is usually mixed with appropriate organic or mineral carriers such as kaolin, synthetic or natural siliceous earth, bentonite, talc, cereal flour or flour from tree bark or from walnut shells, with solvents or diluents such as water, methyl or ethyl alcohol, Ethy-

lenglycol and with surface-active emulsifiers, dispersants and wetting agents such as ammonium salts, salts of alkali metals or alkaline earth metals, Li-gninsulfonic acids, alkyl or arylsulfone derivatives, N-methylamine derivatives or addition products of ethylene oxide to fatty alcohols, mixed aliphatic amines or higher aromatic amines or higher aromatic amines. Other additives, such as buffering agents, diluents, adhesives, anti-foaming agents, dyes and can also be added to the finished agents.

The agent according to the invention can be contained in plastics for forming casings for the seed. It can also be used as an additive for paints, varnishes and other plastics as protection against the destructive effects of fungi.

Another advantage of the agent according to the invention is its ease of use, which results from the water solubility of the compound which form the active ingredient of the agent, while at the same time being more effective than known fungicides. The good water solubility enables the agent to be absorbed by the plants and thus the system effect. An additional advantage of the agent is the broad spectrum of action on the pathogenic substances, which is expressed in the simultaneous effective suppression of the growth of some types of bacteria.

example 1

10 parts of N-dodecyl-N-ethyl-N- (2-hydroxyethyl) - N- (2-methoxy-5- (ß-nitro-ß-methyl-vinyl) benzyl) ammonium chloride were added with 0.3 part Mixed alkylaryl polyglycol ether and 89.7 parts distilled water.

The liquid agent prepared in this way was examined at a concentration of the active ingredient of 1 to 10 ppm and it very effectively suppressed the spore germination of the fungi Alternaria tenuis and Botrytis cinerea.

5

635327

In an experiment on Ross-1 meat chickens, the above-mentioned active ingredient (compound I) was mixed into the same standard compound feed BR-1 in graduated amounts of 10.20, 50 and 100 mg / kg of the compound feed. During the first 4 weeks of the test fattening, a weight gain of 5.6%, 8.5% (statistically significant), 8.6% (statistically significant) and 5.6% compared to the control group was recorded, corresponding to the individual active ingredient doses, and an improvement analogous to feed conversion by 0.9 to 5.3%.

Example 4

The commercially available complete standard compound feed COS-2 for the early rearing of piglets was enriched by adding 1% by weight of the mixture of specifically active additives of the following composition:

2-formylquinoxaline-1,4-dioxide

cyanoacetylhydrazone (Compound I) 5000 mg

Vitamin A 800,000 IU

Vitamin D3 200,000 IU Vitamin B2 300 mg 2o Vitamin B6 100 mg

Vitamin K3 150 mg

Vitamin E 3000 mg

Vitamin C 10,000 mg

Niacin 1000 mg

Calcium pantothenate 500 mg

Lysine 50,000 mg

Ethoxyquin 12,000 mg

When feed mixtures obtained in this way were fed to early weaned piglets during the test period of 28 days, a statistically significant increase in the daily weight gain of 44.1% compared to the control group and an improvement in the feed conversion rate of 20.9% were observed in the first experiment. Similarly, in another experiment, a statistically significant increase in weight gain of 39.9% and an improvement in feed conversion by 33.7% were achieved in comparison to the control animals. In addition, in the experimental group fed with the addition of the active ingredient (compound I) according to the invention, no diarrhea occurred after weaning of the piglets, and in both series of experiments the animals had a high useful performance.